Interfacial Molecular Doping at Donor and Acceptor Interface in Bilayer Organic Solar Cells

Molecular doping is an effective means to tune the optoelectronic properties of organic semiconductors. Despite its versatility, its application in bulk heterojunction (BHJ) organic solar cells (OSCs) is still limited, especially blend‐cast doping. Difficulties in desolving molecular dopants in weakly polar solvents have led to the formation of undesired structures, with relatively high concentrations of dopants affecting the bicontinuous BHJ morphology. Bilayer OSCs are stacked structures with sequential deposition of donor and acceptor films, which make important contributions to the fine tuning of morphology and balanced charge transport. The sequential deposition of thin films in bilayer devices organically facilitates the sequential doping of pure donor polymers by dopants. The sequential doping of the dopant at the interface between the donor and the acceptor can efficiently improve the carrier mobility and the charge transfer between the donor and the acceptor without damaging the quality of the film, thus improving the device performance efficiently. With three different dopants F4TCNQ, F6TCNNQ, and BCF, sequential interfacial doping in bilayer devices is found to be a versatile and effective method to improve device performance. Making this simple doping strategy promising for high‐performance bilayer OSCs, it is evaluated as a promising alternative to BHJ OSCs.